CN1081706A

CN1081706A - Improve the lubricant of erosion resistance

Info

Publication number: CN1081706A
Application number: CN93108075A
Authority: CN
Inventors: T·B·帕维朗; J·L·拉特; B·R·多何纳
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1992-07-08
Filing date: 1993-07-05
Publication date: 1994-02-09
Also published as: US5308521A; DE69311215T2; ZA934814B; AU657225B2; JPH06158075A; IL106236A0; MX9304123A; AU4157893A; DE69311215D1; BR9302347A; EP0578490A1; IL106236A; TW269709B; EP0578490B1; CA2099802A1; ATE154069T1

Abstract

A kind of containing (a) replaces aromatic triazole and (b) compositions of additives and the boron compound reaction of hydrocarbyl substituted succinic acylated polyamine dispersion agent, and the erosion resistance of the lubricating oil that contains the multiple-effect olefin copolymer vi modifiers is improved.

Description

Improve the lubricant of erosion resistance

The present invention relates to a kind of lubricant compositions that improves processing property.

Improve lubricant compositions such as the physics of engine oil and the object that chemical property has become many researchs.For example, used various viscosity indexs (VI) improving agent for many years for making lubricating oil under high and low service temperature, suitable viscosity be arranged all.Their normally various polymkeric substance.New improved VI improving agent is constantly released.The damage of lubricating component in order to prevent, the effect of the corrosive byproducts that generates of particularly being subjected to burning also needs inhibiter in lubricant, and in many cases, these additives and other lubricant additive interact in uncertain mode.For example, when the VI improving agent of some VI improving agent, particularly nitrogenous dispersion agent uses with conventional composite corrosion inhibitor, corrodibility is increased.But found a kind of corrosion inhibitor formula now, when using these selected viscosity index improvers, it can improve its corrodibility.

United States Patent (USP) 3,087,936(Le Suer, April 30,1963) compound and the reaction of a kind of amine with a kind of aliphatic olefin hydrocarbon polymer-generation succsinic acid are disclosed, product and a kind of boron compound that obtains reacted the reaction product that generates.Said composition can be used as lubricant additive.

United States Patent (USP) 4,522,785(D Errico, Junell, 1985) disclose dialkyl amino ylmethyl aromatic triazole and can be used as inhibiter.

United States Patent (USP) 5,049,293(Blain etc., September17,1991) a kind of lubricant or fuel composition additive are disclosed, it is made up of the reaction product of the boronation of succinimide, aldehyde and the triazole of polyalkenyl replacement.Succinimide, aldehyde and the triazole that replaces reacted under 100-200 ℃, normal pressure.Carrying out boronation with for example acid reaction subsequently handles.

United States Patent (USP) 4,948, people such as 542(Kapuscincki, August14,1990) a kind of dispersion antioxygen VI improving agent of lubricating oil composition disclosed.This additive is by a kind of ethene and at least a C ₃-C ₁₀The polymkeric substance that α-monoolefine makes and a kind of nitrosodiphenylamine compound react and prepare.

The present invention proposes a kind of lubricant compositions; it contains oil product that lubricant viscosity is arranged in a large number, a small amount of multiple-effect olefin copolymer vi modifiers and a small amount of additive composition, and said composition contains (a) a kind of aromatic triazole and (b) reaction product of the acylating agent, a polyamine species and the boron compound that replace of a kind of alkyl.

The oil product that lubricant viscosity is arranged.The primary component of the present invention is a kind of oil product that lubricant viscosity is arranged, and comprises natural and ucon oil and their mixture.Natural lubricating oil comprises that animal oil, the oil of planting, alkane belong to, cycloalkanes belongs to and the mixed type mineral lubricating oils, through solvent or acid-treated mineral oil and the oil product that obtains from coal or shale.Ucon oil comprises hydrocarbon ils, halo hydrocarbon ils, alkylene oxide polymer (comprising the polymkeric substance that is made by oxyethane or propylene oxide polymerization), various alcohol (comprising polyvalent alcohol) and the ester of ester, polyvalent alcohol and the monocarboxylic acid of di-carboxylic acid, ester, tetrahydrofuran polymer and the silicone oil (comprising silicone oil and silicic acid ester oil) of phosphoric acid.These oil can be unpurified, purified and re-refining.At United States Patent (USP) 4,326, having introduced these in 972 has the specific examples of lubricated oil product.

In the present invention, lubricating oil generally accounts for major part in composition.For example it generally is the 50%(weight of composition at least), preferably account for about 83% to about 98%; Most preferably account for about 88% to about 90%.But as another selective embodiment, the present invention can provide a kind of additive concentrating liquid, wherein You weight accounts for 0 to 20%(weight), be preferably 1 to 10%(weight) about, and corresponding other component that increased, these components will be introduced below in detail.

Viscosity index improver.Second kind of component of the present invention is a kind of multiple-effect olefin copolymer vi modifiers, and its content is less.The conventional content of this material in final lubricant compositions is about 0.1% to about 15%(weight), be preferably about 0.5% to about 10%(weight), preferably about 1% arrives about 5%(weight).For ease of transportation, this material can provide with the form that contains certain proportion thinning oil or other inert substance as all substances of the present invention.If like this, the total amount of material should suitably be adjusted so that the active ingredient of aequum to be provided.

The multiple-effect olefin copolymer vi modifiers is the mixture of a kind of polymkeric substance or multiple polymers, can play several effects.They at first play viscosity index (" VI ") improving agent.The viscosity with temperature of everybody sight-feed lubricator agent of being familiar with that Here it is and the amount that changes and the effect of speed.These materials have less thickening power when low temperature, significant thickening power is then arranged during high temperature.This performance can enlarge the temperature range that lubricant uses.

Be specially adapted to VI improving agent of the present invention and also can further contain some functional groups that dispersion agent and oxidation inhibitor function are provided to lubricant compositions.The dispersion agent function can prevent that the granulometric impurity in oil or the lubricant is gathered into macrobead and is precipitated as mud or paint film.The oxidation inhibitor function is to prevent that oxygen and lubricant in the atmosphere from interacting, particularly under high temperature and agitation condition.Such function can delay because thickening of oxidation lubricant and acidity increase.Although also can use dispersing additive and antioxidant additive respectively.But still wish usually in VI improving agent structure, to exist one or more to play the comonomer of these functions.

The interested especially VI improving agent of the present invention be graft modification contain the amine olefin copolymer.This olefin copolymer is preferably ethene and alhpa olefin (as butylene, amylene, hexene etc. up to C ₁₂Alpha-olefin, preferably propylene) multipolymer.In polymeric chain, the amount of ethylene copolymer better is about 35% to about 90%(mole), preferably about 40% arrives about 80%(mole), the viscosity-average molecular weight of polymkeric substance is preferably about 5000 to about 500,000, preferably about 150,000 to about 300,000.

Olefin copolymer is introduced the amine functionality by graft reaction and is carried out modification.Graft reaction can react with the free radical grafting of knowing, and for example wherein radical source such as dicumyl peroxide can be extracted a hydrogen atom out from polymeric chain, stay next free radical then.Free radical on the chain can belong to unsaturated point with the monomeric ethene of graft copolymerization and react to each other, and makes comonomer be added on the chain.In addition, a kind of grafting can be undertaken by the reaction of " alkene ".Undersaturated in the method comonomer reacts by ring reaction and the unsaturated part on the polymer chain, makes monomer-grafted.Unsaturated part on the copolymer chain can be the by product in the initial polyreaction, perhaps can be by introducing with the copolyreaction of diene such as 1,3-butadiene or norbornadiene.If need also can have other monomer to exist; If desired, the also available partial oxidation reaction of polymkeric substance or other method are handled, to increase the active site number.

Can also adopt other grafting method, for example ionic graft reaction or react by means of the other active site that the graft copolymerization monomer contains itself.This active site is last to react with second monomer, and this monomer can be the VI improving agent actual required oxidation inhibitor and dispersion agent functionality is provided.

Be suitable for the monomeric example of grafted and comprise some reactive monomers, belong to unsaturated acidylate monomer, p-chloromethyl styrene, ethyl isocyanate, glycidyl methacrylate or methacrylic acid isonitrile acetoacetic ester as amino propylene, maleic anhydride or other ethene.These monomer self-polymerizations and combination generate functional compound, as any first sulfo-aniline, 4-aminodiphenylamine, N-aryl-Ursol D (as N-phenyl-Ursol D), aminocarbazole, amino indole, Aminoindazole quinoline ketone, ammonia mercapto-triazole, amino tetrazole, aminothiazole, aminobenzothiazole, aminoalkyl thiazole, amino-pyrroles, aminopyrimidine or their homologue that replaces of alkyl.The other example of this base polymer is at United States Patent (USP) 5,075,383 and 4,863,623 and European patent bulletin 461774 open.Also can announce 470698 disclosed methods, carry out ligation with oxypolymer and aldehyde source and aromatic polyamine by European patent; Also can be by United States Patent (USP) 4,904,404 disclosed methods are carried out ligation with grafted monomer that contains epoxy group(ing) and the Mannich alkali that is formed by aldehyde, polyamines and phenol.The other functional monomer can be directly grafted on the polymeric chain, comprise alkyl methyl, acrylamide, vinyl pyridine, nitrosoaniline, thiodiphenylamine, N-vinyl pyrrolidone, l-vinyl-2-pyrrolidone, 5-methyl-6-vinyl-1,2,4-thiazine, 4-methyl-5-vinylthiazole, the alkyl substituent of this compounds and their homologue.At United States Patent (USP) 4,948, preferred this base polymer is disclosed in 524.

Texaco chemical company provides a kind of such polymer viscosity index improver, and its commodity are called TLA7700 ^TMThis additive contain useful contain the ethylene-propylene copolymer of amino comonomer or oxidation inhibitor is provided and the functionality of dispersion agent character as active ingredient.(additive that is provided also contains thinning oil, will not calculate.Can think provides the amine functionality by graft copolymer monomer nitrosodiphenylamine.But as the situation of many lubricant additives, thisly some harmful character under some test conditions, can occur, must remedy with one or another kind of method with other relevant additive.Detect by " L-38 " test, have found that when this multi-purpose amine grafted olefin copolymer vi modifiers and be added in the lubricating oil lubricant as motor car engine, and when using with the conventional additives prescription, lubricant can be increased to unacceptable degree to the corrosion of copper-plumbous bearing." L-38 " test is a kind of test method that is used for detecting base chamber oxidation of lubricating oil stability and bearing corrosion.This test is that the running of single cylinder spark fuel injection engine after 40 hours, is measured the weight loss of copper-plumbous connecting rod bearing.This test method is at " lubricant additive " (" Lubricant Additives ", C.V.Smalheer and R.Keunedy Smith(Lesius-Hiles Company Publishers, Cleveland, Ohio, 1967) in the 51st on detailed introduction is arranged.In federal test method standard No.791a, further make stipulations.Therefore, when adopting above-mentioned viscosity index improver, though also do not know the reason that corrodibility increases, can think since on polymer chain substituent chemical property, or because in the preparation graft copolymer process residual chemicals of special additive or generation causes.The present invention proposes a kind of compositions of additives, and it can reduce the corrodibility of the lubricating oil that contains these multiple-effect VI improving agents, so that the lubricating composition of strict preparation can be tested as " L-38 " by commerical test.

Triazole (a).First component of compositions of additives of the present invention is (a) a kind of aromatic triazole.Known have various aromatic triazole, wherein many preparation methods together with them are at " benzotriazole: a kind of novel additive synthesis " (" Benzotriazole:A Novel Synthetic Auxiliary " Katritsky, Rachwal and Hitchings, tetrahedron, Vol47 No.16/17, PP2683-2732,1991(Pergamon Press PLc)) in the literary composition detailed introduction is arranged.

Triazole is a kind of benzotriazole of replacement preferably, and its purpose is to make the solvability of this material in lubricating oil to be enough to make composition to be easy to preparation, to store and to use.Therefore the triazole that preferably contains hydrocarbyl substituent.The position that replaces is not limit.Be on phenyl ring, to replace in one embodiment.In this case, 1 to 4 hydrocarbyl substituent can be arranged, but the most frequently used be a hydrocarbyl substituent.Hydrocarbyl substituent is alkyl, aryl or aralkyl substituting group preferably, and the most frequently used is alkyl.Alkyl comprises from methyl and to comprise ethyl, propyl group, butyl, amyl group, hexyl and heptyl (can be straight or branched) up to chain alkyl such as alkyl oligopolymer or polymkeric substance, and long alkyl chain length such as C ₁₂To C ₂₄Alkyl comprises C ₁₈Alkyl, they can be saturated or unsaturated.The example of the aromatic triazole that is suitable for is benzotriazole alkyl substituted benzene and triazole such as tolyl-triazole, ethyl benzotriazole, hexyl benzotriazole, octyl group benzotriazole etc.), the benzotriazole that replaces of aryl-substituted and triazole (as the phenol benzotriazole etc.) and alkaryl or aralkyl, also can be that substituting group is the replacement benzotriazole of hydroxyl, alkoxyl group, halogen atom (particularly chlorine), nitro, carboxyl and carboxyl alkoxyl group.Top-priority triazole is benzotriazole or alkyl benzotriazole, and alkyl wherein contains 1 to 20 carbon atom, is preferably 1 to 8 carbon atom.What override was considered is benzotriazole and tolyl-triazole.

In the another one embodiment, at least one nitrogen-atoms of triazolyl, replacement is arranged, it is to generate a kind of salt, the preferably salt of benzotriazole negatively charged ion and quaternary ammonium cation that a class replaces like this.For making this salt that hydrocarbon solvability preferably be arranged, the preferred quaternary ammonium cation of considering is by a kind of at least one above-mentioned alkyl that contains, and preferably at least one is no less than that the amine of the alkyl of 6 carbon atoms obtains.Two (2-ethylhexyl) amine is to be suitable for forming this cationic amine.

In addition, the substitution reaction on nitrogen-atoms also can be undertaken by the method that benzotriazole and aldehyde and uncle or secondary amine or alcohol are reacted in the triazole.The example of many such substituted triazoles is disclosed in above-mentioned Katritz-ty reference.

In this embodiment of preparation component (a), used aldehyde can be to contain 1 aldehyde to alkyl, aryl, alkaryl or the aralkyl of about 12 or more carbon atoms.Comprise phenyl aldehyde, salicylic aldehyde and 2-ethyl hexanal.Provide the hydrocarbon dissolubility if wish aldehyde part itself to triazole, should select the suitably bigger aldehyde of carbonatoms so, as have 4 or preferably have the aldehyde of 6 carbon atoms at least at least.But uncle or secondary amine or alcohol reactant also can make molecule obtain most hydrocarbon dissolubility.In this case, be suitable for lower molecular weight aldehyde, preferably formaldehyde and paraformaldehyde.

In the embodiment of component (a) preparation, used amine can be we or a multiple monoamine or a polyamines.These monoamines or polyamines can be primary amine, preferably secondary amine.(as required product is quaternary amine rather than covalent bond structure, it is believed that also to use tertiary amine).

Monoamine generally contains 1 to about 24 carbon atoms, is preferably 1 to about 12 carbon atoms, and preferably 1 to about 6 carbon atoms.The example that is used for monoamine of the present invention comprises methylamine, ethamine, propylamine, butylamine, octylame and n-Laurylamine.The example of secondary amine comprises dimethylamine, diethylamine, dipropyl amine, dibutylamine, first butylamine, second hexylamine etc.Polyamines can be aliphatic series, alicyclic, heterocycle or aromatic polyamine.The example of polyamines comprises alkylene polyamine and heterocyclic polyamines.

Alkylene polyamine is represented with following formula:

The mean value of n is between about 1 to about 10 in the formula, and preferably about 2 to about 7; Alkylidene group has 1 to about 10 carbon atoms, and preferably about 2 to about 6 carbon atoms.R ₄Can be hydrogen atom or alkyl independently, but the aliphatic group that replaces of aliphatic series or hydroxyl preferably, its carbon subnumber can reach 30.

Such alkylene polyamine comprises the methylene radical polyamines.Ethylidene polyamines, butylidene polyamines, propylidene polyamines, pentylidene polyamines etc.Also comprise higher homologue and corresponding heterocyclic amine, as the piperazine of piperazine and the replacement of N-aminoalkyl group.The specific examples of these polyamines be quadrol, diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), three (2-amino-ethyl) amine, propylene diamine, trimethylene diamines, tri propylidene tetramine; Tetren (TEPA), six ethylidene, seven amine, penten etc.

The higher homologue that is obtained by two or more above-mentioned alkylene amines condensations also is an available, and they are mixtures of two or more above-mentioned polyamines.

Can adopt aforesaid ethylidene polyamines.Show " chemical technology encyclopaedia " (" Ency Clopedia of Chemical Techology " at Kirk Othmer.2d, Edition, Vol.7 22-37 page or leaf, Interscience Publishers, New York(1965)) in " ethyleneamines " clauses and subclauses this polyamine species is had detailed introduction.The preparation of this polyamine species is very easy to, and can react by ethylene dichloride and ammoniacal liquor, or react by piperazine and open loop reagent such as water, ammonia etc. and to prepare.These reactions can generate the complex mixture of polyalkylene polyamine, comprise cyclic condensation product such as piperazine.The ethylidene polyamine mixture also can use.

Amine also can be heterocyclic polyamines.These heterocyclic polyaminess are ethylenimine, azetidine, cough up alkane, four and dihydropyridine, pyrroles, indoles, piperidines, imidazoles, two and imidazolidine, piperazine, isoindole, purine, morpholine, thiomorpholine, N-aminoalkyl group morpholine, N-aminoalkyl group thiomorpholine, N-aminoalkyl piperazine, N, N '-Diaminoalkyl piperazine, azepine

, azocine, azonine, azecine and above-mentioned every kind of compound the mixture of four, two and perhydro derivative and two or more these heterocyclic amines.Preferable heterocyclic amine is saturated five or the hexa-member heterocycle amine, particularly piperidines that have only nitrogen, oxygen and/or sulphur on heterocycle, piperazine, thiomorpholine, morpholine, tetramethyleneimine etc.Preferably piperidines, the piperidines of aminoalkyl replacement, piperazine, aminoalkyl substituted-piperazinyl, morpholine, aminoalkyl replace morpholine, tetramethyleneimine and aminoalkyl substituted pyrrolidin.Usually the aminoalkyl substituting group is to replace on the heterocyclic nitrogen-atoms.The specific examples of these heterocyclic amines comprises N-aminopropyl morpholine, N-aminoethyl piperazine and N, N '-diaminoethyl piperazine.

A used other class polyamine mixture is the blended that the residue (being commonly referred to " polyamines residue ") that stays behind the above-mentioned polyamine mixture stripping obtains.Usually, the alkylene polyamine residue only contains and is less than 2%, generally is to be less than 1%(weight) material of boiling point under about 200 ℃.By road (DOW) chemical company (it is 1.0168 at 15.6 ℃ of following proportions for Freeport, the typical sample of this ethylidene polyamines residue that is called " E-100 " that Taxas) obtains, and nitrogen content is a 33.15%(weight), the viscosity in the time of 40 ℃ is 121 centistokes.Gas chromatographic analysis shows, this sample contains have an appointment 0.93% " lighting end " (being likely DETA), 0.72%TETA, 21.74% tetren and 76.61% penten and higher amine (more than be weight percent).These alkylene polyamine residues comprise the higher homologue of cyclic condensation product such as piperazine and diethylenetriamine, Triethylenetetramine (TETA) etc.

Another useful polyamines is at least a oxy-compound and a kind of condensation reaction products that contains between at least one uncle or the polyamines of secondary amino group.Oxy-compound preferably contains 2 to about 10 hydroxyls, and preferably 2 to about 6 hydroxyls, and preferably 2 to about 4 hydroxyls, and the carbonatoms of aliphatic series can reach 40, is preferably 2 to about 30, preferably 2 polyvalent alcohols to about 10 carbon atoms.Polyvalent alcohol comprises ethylene glycol, propylene glycol, glycerol, butyleneglycol, hexylene glycol, sorbyl alcohol, arabitol, mannitol, sucrose, fructose, glucose, cyclohexanediol, tetrahydroxybutane and tetramethylolmethane.Preferable oxy-compound is many azanols, comprises the reaction product of any above-mentioned monoamine and oxirane.The example of many azanols comprises tripropanolamine, three (methylol) aminomethane, 2-amino-2-methyl-1, ammediol, N, N, N ' N '-four (2-hydroxypropyl) quadrol and N, N, N ' N '-four (2-hydroxyethyl) quadrol, preferably three (methylol) aminomethane (THAM).

The polyamine reactant that is suitable for comprises the mixture of Triethylenetetramine (TETA) (TETA), tetren (TEPA), penten and polyamines, as above-mentioned " amine residue ".

Equally, can replace amine and triazole and aldehyde formation reaction product with alcohol.The alcohol that is suitable for comprises straight or branched alcohol, can comprise alkyl carbon chain and contain aromatic ring or the carbochain of heteroatoms (as oxygen or nitrogen).Preferable alcohol is to contain preferably about 4 alcohol to about 24 carbon atoms from 3(, comprises propyl alcohol, butanols, amylalcohol, hexanol (as 4-methyl-2-amylalcohol), octanol (as 2-Ethylhexyl Alcohol) and decyl alcohol.The alcohol of 6 or more carbon atoms preferably is because these materials can make substituted triazole that good oil soluble is arranged.The activity of primary alconol is the highest, thereby optimum is used for preparing this kind product.Secondary by contrast and the tertiary alcohol are considered to relative non-activity.

Component (a) material can be represented by the formula preferably:

R in the formula ₁Be alkyl, n is 0 to 4, condition be if n greater than 1, not all alkyl all must be identical.Preferably n=1 and R ₁Be methyl, therefore such triazole is a tolyl-triazole.

In following formula, R ²And R ³Be hydrogen or alkyl, as long as R ²And R ³Be not hydrogen simultaneously.Be NR ₂R ₃Basis representation uncle or secondary amine residue, but be not ammonia.At one preferably in the embodiment, R ₂And R ₃All be the 2-ethylhexyl, promptly amine is two (2-ethylhexyl) amine.

In following formula, R ⁴It is the alkyl of hydrogen atom or 1 to 6 carbon atom.CHR ⁴Group is equivalent to the residue of an aldehyde, and this aldehyde radical can be at condensation course as described below in order to this preferred material of preparation.Aldehyde is a formaldehyde or its Equivalent preferably.In this case, CH ₄R ⁴Base is CH ₂

Can be with the described adducts of component (a) above the preparation of following method: triazole and amine are mixed in suitable inert solvent, and also water cools off mixture then in ice bath as required.The aqueous solution of aldehyde is added drop-wise in the refrigerative mixture.Usually be preferably the aldehyde and the amine that use the Theoretical Calculation amount that is slightly larger than (general excessive 10 to 20%).It is at once highly beneficial that this is reflected at heating power, and particularly when aldehyde is formaldehyde or paraformaldehyde, reaction can be carried out under room temperature or lower temperature.But in order to remove the water that dereaction generates, being heated to 100 ℃ or higher temperature may wish.

The dispersion agent of boronation (b).Component of the present invention (b) is the reaction product of acylating agent, polyamines and the boride of alkyl replacement.

The acylating agent that alkyl replaces comprises succinic acylating agent) particularly succsinic acid, amber carboxylic acid halides, succinate and succinyl oxide, be preferably acid, ester or acid anhydride, preferably acid anhydride.The carbonatoms mean value that alkyl contains usually is preferably about 30 to about 200, preferably about 35 to about 100 at least 8 to about 350.In one embodiment, alkyl is obtained by polyolefine.

These polyolefinic characteristics are its Mn(number-average molecular weight) be at least about 500.In general, polyolefinic characteristics are that Mn is about 500 to about 5000, are preferably about 700 to about 2500, preferably about 800 and arrive approximately 2000, and what preferentially select for use is about 900 to about 1500.In an other embodiment, Mn changes between about 1200 or 1300 about 500,700 or 800.

Polyolefine comprises 2 to about 16, or to about 6, but or to the monomeric homopolymer of polyolefine and the multipolymer of about 4 carbon atoms.Alkene can be monoolefine such as ethene, propylene, 1-butylene, iso-butylene and 1-octene, or multi-olefin monomer, comprises diolefinic monomer such as 1,3-butadiene and isoprene.At United States Patent (USP) 4,234, introduced the preparation and the application of the succinic acylating agent that replaces in 435, substituting group is wherein obtained by these polyolefine.

In another embodiment; the preparation method of succinic acylating agent is with above-mentioned polyolefine and excessive maleic anhydride reaction, the succinic acylating agent that obtains replacing, and wherein succinyl-group number is at least 1.3 to about 1.5 in the amount substituting group; or to about 1.7, or to about 1.8.Maximum is no more than 4.5 usually, or to about 2.5, or to about 2.1, or to about 2.0.

In another embodiment, the mean value of the carbonatoms that alkyl is contained is from about 8, or about 10, or about 12 up to about 40, or to about 30, or to about 24, or to about 20.In one embodiment, the mean value from about 16 to about 18 of alkyl institute carbon atom quantity.In another embodiment, the mean value 3 to 4 of the contained monomeric unit of alkyl, monomer wherein are iso-butylene or different propylene.In such embodiment, alkyl is a tetrapropylene base.

The preparation method of succinic acylating agent is: with above-mentioned alkene, isomerizing olefins or their oligopolymer and undersaturated carboxylic acid acylating agent such as methylene-succinic acid, methyl-maleic acid, toxilic acid acylating agent about 160 ℃ or about 185 ℃ until about 240 ℃ or to about 210 ℃ under react.The toxilic acid acylating agent is unsaturated preferably acidylate agent.The method that available those industry of the preparation of acylating agent are known; for example at United States Patent (USP) 3; 412; the method of introducing in 111, and people such as Ben shows " alkene reaction of maleic anhydride and alkene " (method of being introduced in " The Ene Reaction of Maleic Anhydride With Alkenes " J.C.S.Perkin II (1977) 535-537 pages or leaves.

The amine that reacts with succinic acylating agent can be any above-mentioned amine of mentioning, is preferably polyamines.Polyamines can be aliphatic, alicyclic, heterocycle or aromatic polyamine.The example of polyamines comprises alkylene polyamine, hydroxyl polyamines, aryl polyamines and heterocyclic polyamines.

Alkylene polyamine is represented with following formula:

N is that mean value is 1 to about 10 in the formula, be about 2 to about 7 preferably, or arrives about 5." alkylidene group " contains 1 to about 10 carbon atoms, preferably about 2 to about 6 or to about 4 carbon atoms.Each R can be the aliphatic group that aliphatic series about hydrogen or carbonatoms to 30 or hydroxyl replace independently.Such alkylene polyamine comprises methylene radical polyamines, ethylidene polyamines, butylidene polyamines, propylidene polyamines, pentylidene polyamines etc.Preferably the ethylidene polyamines is also referred to as polyvinylamine.The preparation of these polyamines is very convenient, ethylene dichloride and ammonia can be reacted, or react with piperazine and open loop reagent such as water, ammonia etc.

The method of the amber dirt amber acid acylating agent that alkyl replaces and the reaction product of amine and this compound of preparation is for example in United States Patent (USP) 4,234,435; 4,952,328; 4,938,881; In 4,957,649 and 4,904,401 introduction is arranged.It is possible that the acylating agent that alkyl of the present invention replaces reacts with the amine of introducing as a triazole part.This product of being generated of reaction, the molecule of its component (a) and (b) is connected with covalent linkage by a shared amine, and United States Patent (USP) 5,049 discloses this material in 293.But in the present invention, pay the utmost attention to component (a) and (b) be independent molecule.

The reaction product of hydrocarbyl substituted succinic acylating agent and amine can further be handled with boron compound.The boron compound that is suitable for comprises boron oxide, boron oxide hydrate, boric acid such as organic boric acid (for example alkyl-B(OH) or aryl-B(OH) ₂), ortho-boric acid (is H ₃BO ₃), tetraboric acid (H ₂B ₄O ₇), metaboric acid (HBO ₂) and the ester of these boric acid.The specific examples of organic boronic comprises methyl-boron-dihydroxide, phenyl-boron dihydroxide, cyclohexyl boric acid, to amylbenzene ylboronic acid and dodecyl boric acid.

Boric acid ester mainly comprises single, two and three organic esters that boric acid and alcohol or phenol generate.Used alcohol or phenol for example are methyl alcohol, ethanol, Virahol, hexalin, cyclopentanol, 1-octanol, sec-n-octyl alcohol, dodecanol, behenyl alcohol, oleyl alcohol, Stearyl alcohol, phenylcarbinol, 2-butyl hexalin, ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,3-butyleneglycol, 2,4-hexylene glycol, 1,2-cyclohexanediol, 1,3-ethohexadiol, glycerol, tetramethylolmethane, 1,4-butyleneglycol, Trivalin SF, Cellosolve ^TM, 1,6-hexylene glycol, 1,9-nonanediol, phenol, naphthols, p-butylphenol, neighbour, right-diheptyl phenol, positive cyclohexylphenol, 2, phenol, ethylene chlorhydrin, ortho chloro phenol, m-nitrophenol, 6-bromine octanol and 7-ketone decyl alcohol that 2-two (to hydroxyphenyl) propane, polyisobutene (molecular weight is 1500) replace.For the present invention, low-carbon alcohol, 1,2-two is pure and mild 1, the 3-glycol, promptly carbonatoms is less than 8 alcohol and is particularly useful for making boric acid ester.Boron compound is ortho-boric acid preferably.

Acylated nitrogen composition and boron compound are easy to react, and these reactants can be mixed under the temperature of hope.The use of inert solvent is chosen wantonly, but in general needs to use, particularly in reaction mixture, exist viscosity higher or solid reactant.Inert solvent can be hydrocarbon such as benzene, toluene, petroleum naphtha, hexanaphthene, normal hexane or mineral oil.Temperature of reaction can change in the larger context.Usually preferably between about 50 ℃ to about 250 ℃, change.Temperature can be 25 ℃ or lower in some cases.The upper limit of temperature is the decomposition temperature of the concrete reaction mixture that uses.

Reaction was finished usually in the short period of time, as 0.6 to 6 hour.After reaction was finished, product may be dissolved in the solvent, and the solution that obtains can be purified with centrifugation or filtering method if appear to have muddiness or contain insolubles.Whether product is normally very pure, does not need further purification, or can select arbitrarily to purify.

Be used to prepare relative proportion between each reactant of boride mainly come according to product purposes in the present invention fixed.About this point, obtain useful product by following reaction mixture.The relative proportion of each reactant is such in this reaction mixture, has an appointment 0.1 boron atom to each nitrogen-atoms of the nitrogenous composition of described employed acidylate 10 boron atoms of having an appointment so that obtain the nitrogenous composition of every mole of used acidylate.It is that the nitrogenous composition of every mole of acidylate is had an appointment 0.5 boron atom to each used nitrogen-atoms 2 boron atoms of having an appointment that each reactant is preferably measured.For instance, the per molecule that has the nitrogenous composition of the acidylate of 5 nitrogen-atoms to use with any per molecule of 1mol has the consumption of boron compound of 1 boron atom greatly between 0.1 to 50mol, preferably from about 0.5 to about 10 moles.Preferably, the relative quantity of each component (b) is the amino and about 2-8mol ortho-boric acid of about 3-5 mole carbonyl, about 2-8 mole, most preferably, relative quantity is the amino and about 2-4 mole ortho-boric acid of about 3～5 moles of carbonyls, about 2-4 mole, at United States Patent (USP) 3, preparation method to these complex compounds in 089,936 has detailed introduction.

In composition, additive combination (a) and adding total amount (b) are about 0.5 to about 10%(weight).Component (a) and relative quantity (b) are that weight is preferably in about 1: 3 to about 1: 120 scope, in preferably about 1: 12 to about 1: 30 scope.The amount normally about 0.001 of component in lubricant compositions (a) is to about 1%(weight), be about about 0.01 preferably to about 0.2%(weight), preferably about 0.03% to about 0.07%(weight).The consumption of component in lubricant compositions (b) is about about 0.1 usually to about 5%(weight), be preferably about 0.3 to about 3%(weight), preferably about 0.6 to 1.5%(weight).The amount of used VI improving agent is about 0.1 to 15%(weight in the final composition), preferably about 0.5 to about 10%(weight), most preferably 1 arrive 5%(weight).The relative quantity that viscosity index improver and component (a) add (b) is preferably about 1: 2 to about 25: 1.

So-called herein " hydrocarbyl substituent " or " alkyl " refer to a kind of group that has a carbon atom directly to link to each other with the rest part of molecule and mainly contain the hydrocarbon characteristic.These groups comprise alkyl, substituted hydrocarbon radical and heteroatom group, and promptly this group contains other atom that is not carbon in chain of mainly being made up of carbon atom or ring, but it still has main hydrocarbon characteristic.

Optional components.Except said components, generally also contain some additives commonly used in lubricant compositions in the composition of the present invention.Concrete which additive of selecting will depend on practical use, but can comprise the salt that one or more basic metal or alkaline-earth metal and acid organism (carboxylic acid, sulfonic acid, phosphonic acids, phenol etc.) form.These salt are considered to the high alkalinity material usually.The high alkalinity material generally is a system in single-phase, the homogeneous, and its characteristics are that the content of metal will be higher than the neutral amount that is used for, and this dosis neutralisata is to draw through stoichiometric calculation according to metal with the specific acid organic matter of metal reaction.The available acidic cpd of the preparation of high alkalinity material (generally is mineral acid or low-grade carboxylic acid, carbonic acid gas preferably) react with a mixture, mixture wherein by acid organism, at least a be that organic solvent inert (mineral oil, petroleum naphtha, toluene, dimethylbenzene etc.), a kind of metal base and a kind of promotor (as phenol or alcohol) greater than stoichiometric quantity are formed to above-mentioned acid organism.Acid organism generally contains abundant carbonatoms makes it that certain dissolubility be arranged in oil.The excessive of metal generally recently represented with metal.So-called " metal ratio " refers to the total yield of metal and the ratio of the organic equivalent of acidity.Its metal ratio of neutral metal-salt is 1.When the metal that salt contains is 4.5 times of normal-salt, excessive 3.5 equivalents of its metal, promptly the metal ratio is 4.5.

Be engaged in these professional personnel and all know these high alkaline compounds.Preparation technology's the patent of introducing the mixture of the basic salt of sulfonic acid, carboxylic acid and any two or more salt comprises United States Patent (USP) 2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162; 3,318,809; 3,488,284 and 3,629,109.

Said composition can also comprise auxiliary sulfur-bearing, phosphorus and sulfur-bearing and phosphorated anti-wear agent.So-called anti-wear agent is meant can give lubricant compositions and the functional liquid material with resistance to abrasion.Anti-wear agent can be used to the control wearing and tearing, also plays extreme pressure and antioxidant effect.These anti-wear agents comprise sulfurized organic compound, phosphoric acid hydrocarbyl carbonate, contain phosphamide, phosphorus-containing carboxylic acid ester, phosphorous ether and the compound that contains dithiocarbamate.The example of phosphoric acid hydrocarbyl carbonate comprises the thiophosphoric acid hydrocarbyl carbonate.Thiophosphatephosphorothioate can contain 1 to about 3 sulphur atoms, is preferably 1 to 2 sulphur atom.The preparation method of thiophosphatephosphorothioate comprises that with one or more phosphorous acid esters and vulcanizing agent sulphur, halogenation sulphur and sulfocompound react.The salt of thiophosphatephosphorothioate comprises phosphorodithioate zinc.

Also available some other oxidation inhibitor, pre-etching agent and extreme pressure anti-wear additives comprise chlorination aliphatic hydrocrbon and molybdenum compound.

Also can contain pour point depressant, they in the lubricating oil that this paper introduced usually as a kind of useful especially additive.For example referring to " lubricant additive " (" Lubricant Additives ", C.V.Smalheer and R.Kennedy Smith, the 8th page of (Lesius Company Publishers, Cleveland, Ohio, (1967)) book.

Also can use kilfoam to reduce or to avoid generating stable foam.It comprises siloxanes or organic polymer.Show the example that 125-162 page or leaf in " Foam Control " (" Foam Control Agents ") (Noyes Data Corporation, 1976) has been introduced these and other some kilfoam composition at Henry T.Kerher.

Some additives of these and other that can contain are at United States Patent (USP) 4,582, and (from 14 row, 52 row to 17 row, 16 row) have more detailed introduction in 618.

Embodiment

With each component by shown in mixed can be following examples and prepare.All contain (a) mentioned above and (b) additive agent mixture among these embodiment, each embodiment has stronger erosion resistance than the analogous composition that does not contain two kinds of components.Some fully-formulated compositions (they contain other additive of many kinds) can be by required anticorrosive commerical test.

Each preparation of compositions method is that each component is mixed:

(per-cent among following each embodiment all is weight percentage)

Embodiment 1:

-(ⅰ) about 94% lubricating base oils;

-(ⅱ) 5%(by active ingredient and deduct thinning oil and calculate) be called Texaco ^TMThe ammonia comonomer grafted ethylene/propene viscosity index improver of TLA7700.It is believed that the amine functionality that this material has the graft copolymerization monomer by N nitrosodiphenyl amine to provide, and molecular weight is about 200,000;

-(a) 0.05% tolyl-triazole and formaldehyde and two (2-ethylhexyl) amine (its commodity are called Reomet by the product of mol ratio condensation in 1: 1: 1 ^TM39);

-(b) 1% polyisobutylene-substituted succinic anhydride and the reacted boration product of polyvinylamine, the mol ratio of CO: N: B is 4: 3: 3.

Embodiment 2:

-(ⅰ) about 97.4% lubricating base oils;

-(ⅱ) 2.5% ammonia comonomer grafted ethylene/propylene/hexadiene viscosity index improver wherein contains the amine functionality that the graft copolymerization monomer by vinyl pyridine provides;

-(a) 0.001% benzotriazole and acetaldehyde and single DEHA be by the product of 1: 1: 1 mol ratio condensation;

-(b) succinyl oxide and the reacted boration product of amine residue, wherein CO: the N that replace of 0.1% polypropylene: the B mol ratio is 3: 8: 2, and the boration product makes by succinylation compound and acid reaction.

Embodiment 3:

-(ⅰ) about 98% blending lubricating base oils (mainly is Texaco ^TMSNO-100 and 150);

-(ⅱ) the monomer-grafted ethylene/propene viscosity index improver of 0.5% amine copolymer, amine functionality is wherein provided by the graft copolymerization monomer of thiodiphenylamine;

-(a) salt of the quaternary ammonium salt of 0.05% tolyl-triazole negatively charged ion and diethylhexyl amine;

-(b) succinyl oxide that replaces of the 1% propylene tetramer and ethyleneamines cell-average number are 8 the reacted boration product of polyvinylamine, CO: N wherein: the B mol ratio is 5: 2: 8, can prepare this product by succinic acid derivative and boric acid isopropyl ester are reacted.

Embodiment 4: the composition of embodiment 1, difference are the l-vinyl-2-pyrrolidone grafted ethylene-butadiene copolymers that viscosity index improver (ⅱ) changes into equivalent.

Embodiment 5: the composition of embodiment 1, difference are ethylene-propylene-norbornadiene multipolymers (mol ratio 70: 29: 1) that viscosity index improver (ⅱ) changes the methyl acrylamide graft of equivalent into.

Embodiment 6: the composition of embodiment 1, add

-(c) calcium salt of the alkylphenol of 2% sulphur coupling is phenol and 3 normal sulphur or the SCl that replaced by the 4 equivalent propylene tetramers ₂What prepare (can prepare about 1 part with S, use SCl ₂Can prepare about 2 parts), contain have an appointment 50% activeconstituents and about 50% inertia thinning oil;

-(d) the high-alkali calcium salt of 3.1% side chain monoalkyl sulfonic acid, molecular weight is about 500, and the metal ratio is 11, and 50% active ingredient and about 50% thinning oil are arranged approximately;

-(e) 2% polyisobutene succinic diamide is reacted with the amine residue by polybutene (1mol) and succinyl oxide (1.8mol) and to obtain, and molecular weight is 2500, and the mol ratio of CO: N is 1: 1; It is 100% that the amount of adjusting lubricating oil makes total composition.

Embodiment 7: the composition among the embodiment 6, difference is that used base oil is the lubricating oil among the embodiment 3, overbased compositions (d) is made up of following compounds: the Phenylsulfonic acid magnesium that about 53% molecular weight is 500, metal replaces than the side chain monoalkyl that is 2.8,19% molecular weight is 500, metal is than the high alkali salt of side chain monoalkyl calcium sulphonate that is 1.2, and about 15% metal is than the high alkali salt of above-mentioned side chain sulfonic acid magnesium that is 11; About 5% metal than be that 11 the high alkali salt of above-mentioned side chain calcium sulphonate and about 8% molecular weight are about 385, metal is than the straight chain and the high alkali salt of side chain dialkyl group sodium sulfonate that are 20, also can comprise:

-(f) the phosphorodithioic acid diester that obtains by Virahol and 4-methyl-2-amylalcohol of 1.8% usefulness zinc oxide neutral.

Embodiment 8: the composition of embodiment 6, difference are that the active ingredient of high alkali composition (d) is 60% the chain alkyl carboxylic acid ester's that is about 18 carbon atoms high-alkali yellow soda ash and 40% C ₉The mixture of the high-alkali magnesiumcarbonate of alkyl phenate.

Embodiment 9: the composition of embodiment 7, and difference is:

The consumption of component (ⅱ) is 10%, and this component is to be provided by the mixture that contains nearly 50% activeconstituents and about 50% thinning oil, obtains the active ingredient of concentration about 5%;

The consumption of component (b) is 1.7%, and this component is provided by the thinning oil of 62% active ingredient and 38%;

The consumption of component (c) is 3.1%;

The consumption of component (d) is 3.9%;

The consumption of component (e) is 4% polyisobutene succinic diamide, and be that 2000 polyisobutene (1mol) and succinyl oxide (2mol) obtain CO with the polyvinylamine reaction by molecular weight: the mol ratio of N is 6: 5,45% active ingredient, 55% thinning oil;

The consumption of component (f) is 1.2%;

And can contain following component:

-(g) 0.3% mixes single and dialkyl groupization (C ₉) p-diaminodiphenyl (containing 16% thinning oil);

-(h) 0.2% sulfurized carboxylic acid tetrahydrobenzene butyl ester, the mol ratio of alkene and sulphur is about 1: 1(contains 5% thinning oil);

-(i) 0.15% oleylamide C ₁₇H ₃₃CONH ₂; And

-(j) every kind be less than other additive of 0.1%, comprise siloxanes kilfoam and pour point depressant.

Embodiment 10: the composition of embodiment 9, and not existing together is that component (ⅱ) is to use the acid anhydride-grafted ethene of horse and the multipolymer of propylene, grafted acid anhydride comonomer further reacts (mol ratio of acid anhydride and pentanoic is 1: 1) with the 6-aminodiphenylamine.

Embodiment 11: the composition of embodiment 9, not existing together is that high alkaline constituents (d) is the high-alkali sodium salt of the dialkyl group sulfonate of component d(insatiable hunger straight chain among 3% embodiment 7 and side chain) and 0.8% embodiment 8 in component (d).

Embodiment 12: the composition of embodiment 1, and not existing together is that component (a) is a tolyl-triazole, its content is about 0.1%.

Embodiment 13: the composition of embodiment 6, and not existing together is that component (a) is the tolyl-triazole amine salt, its structure is:

R=oil base in the formula.

Embodiment 14: the composition of embodiment 9, do not exist together that to be component (a) press the condensation product of 1: 1: 1 mol ratio for tolyl-triazole and formaldehyde and tridecyl alcohol, and its molecular formula is:

Every kind of above-mentioned data is incorporated the present invention into as a reference at this.Used herein " basically by ... form " refer to contain the material of characteristic of the fundamental sum novelty of the composition that does not in fact influence research on a small quantity.

Claims

1, a kind of lubricant compositions of forming by following substances: the oil product of lubricant viscosity, a small amount of multiple-effect olefin copolymer vi modifiers and a small amount of additive composition are arranged in a large number, the consisting of of compositions of additives:

(a) a kind of aromatic triazole and

(b) a kind of reaction product of acylating agent, a polyamine species and a kind of boron compound of alkyl replacement.

2, according to the composition of claim 1, wherein olefin copolymer can provide dispersed and the monomer-grafted ethene of antioxygen and the multipolymer of propylene for using.

3, according to the composition of claim 1, wherein comonomer is the nitroso-group diaryl-amine.

4, according to the composition of claim 1, wherein aromatic triazole is a kind of benzotriazole of replacement.

5, according to the composition of claim 4, wherein benzotriazole is replaced by hydrocarbyl substituent on phenyl ring.

6, according to the composition of claim 4, wherein benzotriazole is substituted on a nitrogen-atoms.

7, according to the composition of claim 6, wherein benzotriazole is a kind of benzotriazole negatively charged ion and by the derive salt of the quaternary ammonium cation that obtains of a kind of alkylamine that contains 6 carbon atoms at least.

8, according to the composition of claim 6, wherein the replacement of benzotriazole on a nitrogen-atoms is by carrying out benzotriazole and a kind of aldehyde and a kind of uncle or secondary amine or a kind of alcohol reaction.

9, according to the composition of claim 8, wherein benzotriazole and a kind of aldehyde and a kind of uncle or secondary amine react.

10, according to the composition of claim 1, wherein the triazole in (a) is:

R in the formula ¹Be an alkyl,

N is 0 to 4, if n greater than 1, the structure of not all this alkyl all needs identical;

R ²And R ³Be hydrogen or alkyl, but R ²And R ³Can not all be hydrogen; And

R ⁴Be hydrogen or a kind of alkyl of 1 to 6 carbon atom.

11, according to the composition of claim 10, wherein n is 1 and R ¹It is methyl.

12, according to the composition of claim 10, R wherein ²And R ³It is the 2-ethylhexyl.

13, according to the composition of claim 10, R wherein ⁴Be hydrogen.

14, according to the composition of claim 1, wherein acylating agent is a succinic acylating agent.

15, according to the composition of claim 14, wherein acid acylating agent is a succinyl oxide behind the amber.

16, according to the composition of claim 1, wherein (a) is the reaction product of tolyl-triazole, formaldehyde and two (2-ethylhexyl) amine.

17, according to the composition of claim 1, wherein the hydrocarbyl substituent in (b) is a kind of C ₈To C ₅₀₀Alkyl or the mixture of such alkyl.

18, according to the composition of claim 17, wherein hydrocarbyl substituent is the oligopolymer of an iso-butylene or propylene.

19, according to the composition of claim 1, wherein the average monomer unit number that contains of the hydrocarbyl substituent in (b) is 3 to 4.

20, according to the composition of claim 18, wherein the molecular weight of hydrocarbyl substituent is about 500 to about 2000.

21, according to the composition of claim 20, wherein hydrocarbyl substituent is an isobutene polymer.

22, according to the composition of claim 1, wherein polyamines is a polyethylene polyamines.

23, according to the composition of claim 22, wherein the polyethylene polyamines is on average there being the mixture of 3 to 10 the unitary polyethylene polyamines of ethyleneamines.

24, according to the composition of claim 1, wherein the boron compound in the component (b) is a boric acid.

25, according to the composition of claim 24, wherein the relative quantity of each component is the amino and about 2-8 mole boric acid of about 3-5 mole carboxyl, about 2-8 mole in (b).

26, according to the composition of claim 25, wherein the relative quantity of each component is the amino and about 2-4 mole boric acid of about 3-5 mole carboxyl, about 2-4 mole in (b).

27, according to the composition of claim 1, wherein (a) and weight ratio (b) are about 1: 3 to about 1: 120.

28, according to the composition of claim 27, wherein (a) and weight ratio (b) are about 1: 12 to 1: 30.

29, according to the composition of claim 1, wherein the amount of component (a) is about 0.001 to about 1%(weight), the amount of component (b) is about 0.1 to arrive about 5%(weight).

30, according to the composition of claim 29, wherein the amount of component (a) is about 0.01 to about 0.2%(weight), the amount of component (b) is about 0.3 to arrive about 3%(weight).

31, according to the composition of claim 30, wherein the amount of component (a) is about 0.03 to about 0.07%(weight), the amount of component (b) is about 0.6 to arrive about 1.5%(weight).

32, according to the composition of claim 1, wherein multiple-effect olefin copolymer vi modifiers and binder component (a) add (b) relative weight than being about 1: 2 to about 25: 1.

33, a kind of concentrated solution, this concentrated solution contain a certain proportion of a kind of the have oil product of lubricant viscosity, a kind of multiple-effect olefin copolymer vi conditioning agent and a kind of compositions of additives, and said composition comprises:

(a) a kind of aromatic triazole and